Uniformly dyed water-swellable cellulosic fibers

ABSTRACT

Uniformly dyed water-swellable cellulosic fibers which are fast to washing, dry-cleaning, sublimation and light and have been produced by contacting water-swellable cellulose fibers sequentially or concomitantly with water, ethylene glycol or a derivative thereof and, while the fibers are still swollen, an essentially water-insoluble dye of the formula ##STR1## in which D is the radical of a diazo component; 
     R is hydrogen, C 1  to C 7  alkyl, phenyl or phenyl bearing methyl as a substituent; 
     X is cyano, carbamoyl or substituted carbamoyl; 
     R 1  is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical; 
     R 2  is hydrogen or an aliphatic, cycloaliphatic or araliphatic radical; 
     R 3  and R 4  independently of one another have the same meanings as R 1  and R 2  ; and 
     R 1  --n--r 2  and R 3  --N--R 4  independently of one another are saturated heterocyclic radicals.

This application is a continuation-in-part of our copending application Ser. No. 728,527 filed Oct. 1, 1976.

The invention relates to uniformly dyed water-swellable cellulosic fibers which are fast to washing, dry-cleaning, sublimation and light and have been produced by contacting water-swellable cellulose fibers sequently or concomitantly with water, ethylene glycol or a derivative thereof and, while the fibers are still swollen, an essentially water-insoluble dye of the formula ##STR2## IN WHICH D is the radical of a diazo component;

R is hydrogen, C₁ to C₇ alkyl, phenyl or phenyl bearing methyl as a substituent;

X is cyano, carbamoyl or substituted carbamoyl;

R¹ is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical;

R² is hydrogen or an aliphatic, cycloaliphatic or araliphatic radical;

R³ and R⁴ independently of one another have the same meanings as R¹ and R² ; and

R¹ --n--r² and R³ --N--R⁴ independently of one another are saturated heterocyclic radicals.

The radical D may be derived particularly from an amine of the benzene, naphthalene, benzothiazole, benzoisothiazole, thiazole, thiadiazole, indazole, pyrazole, thiophene, azobenzene, phthalimide, naphthalimide or anthraquinone series.

Examples of substituents of the radical of the diazo component D are: in the benzene series: fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, carboxylic esters such as C₁ to C₈ alkoxycarbonyl, phenoxycarbonyl, phenoxyethoxycarbonyl or β-C₁ to β-C₄ alkoxyethoxycarbonyl, optionally N-monosubstituted or N,N-disubstituted carbamoyl or sulfamoyl, methyl, ethyl, butyl, octyl, hexyl, methoxy or ethoxy and also carboxy. N-substituents of carbamoyl or sulfamoyl are for example methyl, ethyl, phenyl, benzyl, phenylethyl, cyclohexyl, norbornyl, propyl, butyl, β-hydroxyethyl, γ-hydroxypropyl, β-methoxyethyl, γ-methoxypropyl, γ-ethoxypropyl and also pyrrolidide, piperidide and morpholide.

In the azobenzene series: fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, methyl, ethyl, carboxy, methoxy and ethoxy, the carboxylic esters, carbamoyl and sulfamoyl radicals referred to under the benzene series, and hydroxy.

In the heterocyclic series: chloro, bromo, nitro, cyano, methyl, ethyl, phenyl, methoxy, ethoxy, methylmercapto, β-carbomethoxyethylmercapto, β-carboethoxyethylmercapto, carbomethoxy, carboethoxy, acetyl, methylsulfonyl and ethylsulfonyl.

In the anthraquinone series: chloro, bromo, amino, acetyl, methyl, ethyl, phenylamino, tolylamino, hydroxy, methoxy, ethoxy, cyano and carboxy.

In the benzene and naphthalene series diazo components are preferred which have at least one substituent which decreases the basicity such as methylsulfonyl, phenylsulfonyl, ethylsulfonyl, carboxylic ester, optionally N-subtituted carbamoyl, chloro, bromo, trifluoromethyl and particularly cyano.

Radicals R other than hydrogen are for example ethyl, n-propyl, isopropyl, butyl, pentyl, α-ethylpentyl, phenyl or methylphenyl and preferably methyl.

Examples of R¹, other than hydrogen, are the following substituents: alkyl of one to eight carbon atoms, alkyl of two to eight carbon atoms, alkyl of two to eight carbon atoms bearing hydroxy, cyano, alkoxy or one to eight carbon atoms, phenoxy, phenoxyethoxy or benzyloxy as a substituent, cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl, phenylbutyl, phenyl, phenyl bearing chloro, methyl, trifluoromethyl, pyrrolidonyl, methoxy or ethoxy as a substituent,

C₅ to C₁₂ polyalkoxyalkyl,

C₄ to C₉ hydroxypolyalkoxyalkyl,

C₁ to C₈ alkanoyloxy C₂ to C₆ alkyl,

C₇ to C₁₁ aroyloxy C₂ to C₆ alkyl,

C₁ to C₈ alkylaminocarbonyloxy C₂ to C₆ alkyl,

C₆ to C₁₀ arylaminocarbonyloxy C₂ to C₆ alkyl,

C₁ to C₈ alkoxycarbonyl C₂ to C₇ alkyl and

C₁ to C₁₈ alkanoyl, C₈ to C₁₀ aralkanoyl, C₇ to C₁₁ aroyl,

C₁ to C₄ alkylsulfonyl and C₆ to C₁₀ arylsulfonyl.

In addition to those already specified, the following are specific examples of suitable radicals R¹ :

1: unsubstituted or substituted alkyl:

CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, ##STR3## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR4## (CH₂)₄ OH, (CH₂)₆ OH, ##STR5## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN, (CH₂)₇ CN, (CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ CN, (CH₂)₂ O(CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH₂)₃ OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR6## CH₂ CH₂ COOH, (CH₂)₅ COOH, (CH₂)₆ COOH, the corresponding radicals in which the groupings: ##STR7## are present two or three times;

CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₄ H₉, ##STR8## (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇, (CH₂)₃ O--, (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR9##

2. unsubstituted or substituted cycloalkyl and polycycloalkyl: ##STR10##

3. aralkyl:

CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR11## as well as C₆ H₄ CH₃ instead of C₆ H₅ ;

4. unsubstituted or substituted phenyl;

C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OCH₂ CH₂ OH or C₆ H₄ Cl;

5. The radicals CH₂ CH═CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅, (CH₂)₅ COOC₄ H₉, ##STR12## n being 2, 3, 4 or 6.

6. acyloxy: (CH₂)₂ OCHO, (CH₂)₂ OCOCH₃, (C₂ H₄ O)₂ CHO, (C₂ H₄ O)₂ COCH₃, (CH₂)₂ OCOC₃ H₇, ##STR13## (CH₂)₂ OCOC₆ H₅, (CH₂)₂ OCOC₆ H₄ CH₃, (CH₂)₂ OCOC₆ H₄ Cl, (CH₂)₂ OCOC₁₀ H₇, (CH₂)₂ OCONHCH₃, (CH₂)₂ OCONHC₄ H₉, ##STR14## (CH₂)₂ OCONHC₆ H₅, (CH₂)₂ OCONHC₆ H₄ Cl, (CH₂)₂ OCONHC₆ H₃ Cl₂, and the corresponding radicals with (CH₂)₃ ; (CH₂)₄ or (CH₂)₆ in each case.

7. acyl:

CHO, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, ##STR15## C₂ H₅ CO, CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂ and CH₃ C₆ H₄ SO₂.

Examples of preferred substituents are hydrogen, CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, CH₂ CH₂ OH, (CH₂)₃ OH, ##STR16## (CH₂)₄ OH, (CH₂)₆ OH, ##STR17## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR18## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR19## C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₄ OH and (CH₂)₅ COOH. Examples of radicals R¹ --N--R² and R³ --N--R⁴ are: pyrrolidino, piperidino, morpholino, piperazino and hexamethyleneimino.

Dyes of the formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II):

    d--nh.sub.2                                                (ii)

with a coupling component of the formula (III): ##STR20## in which D, R, X, and R¹ to R⁴ have the above meanings.

The amines are diazotized by the usual methods. Coupling is also carried out as usual in an aqueous medium, with or without the addition of a solvent, at a strongly acid to weakly acid pH.

The uniformly dyed fibers of the invention are preferentially obtained with dye formulations which contain, in addition to conventional dispersing agents, water retention agents and water, a dye of the formula (I) in which:

D is phenyl substituted by cyano, trifluoromethyl, methyl, fluoro, chloro, bromo, C₁ to C₄ alkylsulfonyl, phenylsulfonyl, ##STR21## anthraquinonyl; anthraquinonyl substituted by methyl, chloro, bromo or carboxyl; or benzoisothiazolyl substituted by nitro, chloro or bromo;

R is hydrogen, C₁ to C₃ alkyl or phenyl;

X is cyano, carbamoyl or ##STR22## R¹ and R³ independently of one another are hydrogen; C₁ to C₈ alkyl; C₂ to C₈ alkyl substituted by hydroxy, C₁ to C₈ alkoxy, phenoxy, tolyloxy, cyclohexyloxy, benzyloxy, β-phenylethoxy, carboxyl, carboxylic ester with a total of 2 to 9 carbon atoms, carboxylic acyloxy with a total of 1 to 11 carbon atoms, C₁ to C₈ alkylaminocarbonyloxy, benzoylaminocarbonyloxy, tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy, dichlorophenylaminocarbonyloxy or pyrrolidonyl; cyclohexyl; norbornyl; phenyl-C₁ to C₄ -alkyl; tolyl-C₁ to C₄ -alkyl; β-phenyl-β-hydroxy-ethyl; phenyl; phenyl substituted by fluoro, chloro, bromo, methyl, trifluoromethyl, ethyl, methoxy, ethoxy or pyrrolidonyl; CH₂ CH₂ OCH₂ CH₂ OH; or (CH₂)₃ (OC₂ H₄)_(n) OB;

n is zero, 1 or 2;

B is hydrogen, C₁ to C₄ alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or tolyl;

R² and R⁴ independently of one another are hydrogen or C₁ to C₄ alkyl;

R¹ and R² together with the nitrogen are pyrrolidino, piperidino, morpholino or hexamethyleneimino;

T¹ is hydrogen, chloro, bromo or methyl;

T² is hydrogen or methyl;

T³ is hydrogen, ##STR23## or COOB¹ ; B¹ is hydrogen, C₁ to C₈ alkyl, phenyl-C₁ to C₄ -alkyl or (OC₂ H₄)_(n) OB;

Y is --SO₂ -- or --CO--;

T⁴ is hydrogen or chloro; and

T⁵ is hydrogen, methyl or ethyl.

Dye formulations which contain a dye or dye mixture of the formula (Ia): ##STR24## in which D¹ is a diazo component devoid of nitro groups of the benzene, phthalimide, naphthalimide, anthraquinone or azobenzene series or a nitrobenzoisothiazolyl radical;

A is hydrogen or C₁ to C₃ alkyl; and

X¹ is cyano or carbamoyl; and

R¹ and R³ have the meanings given above,

are particularly important industrially.

The substituents are conveniently chosen so that the molecule contains either in the diazo component or in the coupling component at least one aryl radical and preferably a phenyl radical.

We have special preference for A to be methyl and X¹ to be cyano and also for the combination A═H and X¹ =CONH₂.

Dyes are moreover preferred in which at least one of the radicals R¹ and R³ contains an oxygen-containing amine radical, preferably the radical of one of the amines: phenoxyethoxypropylamine, phenoxyethoxyethoxypropylamine, benzyloxypropylamine, phenylethoxypropylamine, butoxyethoxypropylamine, benzoyloxyethylamine, benzoyloxypropylamine, benzoyloxyethoxyethylamine, H₂ N(CH₂)₃ O(CH₂)₄ OCOC₆ H₅, H₂ N(CH₂)₂ OCONHC₆ H₅, H₂ N(CH₂)₃ OCONHC₆ H₅ and H₂ N(CH₂)OCONHC₆ H₄ Cl and the combination of one of these radicals with phenylamino or amino. The radical D¹ may be derived for example specifically from the following amines: o-cyanoaniline, m-cyanoaniline, p-cyanoaniline, 2,4-dicyanoaniline, 2,4,6-tribromoaniline, 2,4-dichloroaniline, 2-cyano-4,6-dibromoaniline, 2,4-dicyano-6-bromoaniline, 4-cyano-2-chloroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-aminobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2-chloro-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, propyl 3,5-dichloroanthranilate, β-methoxyethyl 3,5-dibromoanthranilate, 4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone, 2-aminodiphenylsulfone, 4-aminodiphenylsulfone, 3-aminophthal-β-hydroxyethylimide, 4-aminophthalic phenylimide or p-tolylimide, 3-amino-6-chlorophthalimide and its N-substitution products, 3-amino-4-cyano-5-methylphthalimide and 3-amino-4-cyano-5-ethylphthalimide and their N-substitution products, 1-amino-2-chloroanthraquinone, 1-amino-2-bromoanthraquinone, 1-amino-2,4-dibromoanthraquinone, 1-amino-2-acetyl-4-chloroanthraquinone, 1-aminoanthraquinone-6-carboxylic acid, its ethyl ester, the ethyl ester of 1-aminoanthraquinone-6-carboxylic acid, 1-amino-4-methoxyanthraquinone, 1-amino-4-hydroxyanthraquinone, 1-amino-2-chloro-4-p-toluidinoanthraquinone, 2-amino-1-chloroanthraquinone, 2-amino-3-chloroanthraquinone, 2 -amino-3-bromoanthraquinone, 2-amino-1,3-dibromoanthraquinone, 2-amino-1-cyano-3-bromoanthraquinone,1-aminobenzanthrone, 6-aminobenzanthrone, 7-aminobenzanthrone, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 2,4-dicyano-3,5-dimethylaniline, the imide, methylimide, n-butylimide, 2-hydroxyethylimide, 3'-methoxypropylimide or phenylimide of 4-aminonaphthalic acid, 5-nitro-3-aminobenzoisothiazole-(2,1) or 5-nitro-7-bromo-3-aminobenzoisothiazole-(2,1).

Examples of suitable diazo components of the aminoazobenzene series are: 4-aminoazobenzene, 3-chloro-4-aminoazobenzene, 3-bromo-4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 2-methyl-4',5-dimethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethyl-4-aminoazobenzene, 4'-methoxy-2,5-dimethyl-5-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene, 3-methoxy-4-aminoazobenzene, 2',3-dimethyl-5-bromo-4-azobenzene, 4'-amino-2',5'-dimethylazobenzene-4-sulfonic amide, 4'-amino-2',5'-dimethylazobenzene-4-sulfonic amide and the aminoazobenzenes of the formula: ##STR25## in which T¹ is hydrogen, chloro, bromo or methyl;

T² is hydrogen or methyl; and

T³ is a radical of the formula ##STR26## or --COOB¹ where Y is CO or SO₂ and B¹ is an alcohol radical and R¹ and R² have the meanings given above.

The dyes of the formula (I) may from their constitution be termed disperse dyes whose application for example to cotton is not as a rule possible. A process is described however in U.S. Pat. No. 3,706,525 which makes printing on cellulose and cellulosic textile material possible. Details given therein concerning process conditions are applicable to the dyes of the present invention. Other methods are specified in our copending application Ser. No. 691,496 according to which the dyes according to formula I may be applied. Printing processes are preferred. The above patent and application are incorporated herein by reference.

The dyes according to formula I give dyeings and prints having excellent fastness properties among which wet fastnesses (particularly fastness to washing, water, perspiration and sea water) and in some cases lightfastness may be emphasized. In the case of prints for example no staining of any white ground present occurs in washing.

In the following Examples, which illustrate the invention, parts and percentages are by weight unless specified otherwise.

EXAMPLE 1

Cotton cloth is printed by a rotary screen printing method with an ink consisting of 10 parts of the dye of the formula: ##STR27## 100 parts of polyethylene oxide of a molecular weight of 300 to 790 parts of a 3% alginate thickening and the print is dried at 100° C. The print is then treated for one minute at 200° C. with hot air, rinsed cold, soaped at the boil, again rinsed cold and dried. A light-fast and wash-fast yellow orange print is obtained on a white ground.

EXAMPLE 2

A cloth from a blend of polyester and cotton (ratio by weight 67:35) is printed with a paste consisting of 20 parts of the dye of the formula ##STR28## 120 parts of the reaction product from polyethylene oxide having a molecular weight of 300 with boric acid in the molar ratio 3:1 and 860 parts of a 10% alginate thickening. The print is dried at 105° C. and treated for six minutes at 180° C. with superheated steam. The print is then rinsed with cold water, soaped at 80° C., again rinsed cold and dried.

A red print which is fast to light and washing is obtained on a white ground.

EXAMPLE 3

A cotton cloth is printed by the roller printing method with a print paste consisting of 15 parts of the dye of the formula: ##STR29## 110 parts of polyethylene oxide of the molecular weight 350, 30 parts of the diethanolamide of oleic acid and 845 parts of a 10% alginate thickening. The print is dried at 100° C. and then fixed by a treatment with hot air for one minute at 195° C. The print is finished off as described in Example 1 and a fast orange print is obtained on a white ground.

EXAMPLE 4

Cloth of a blend of polyester and cellulose (ratio by weight 67:35) is printed on a screen printing machine with an ink consisting of 30 parts of the dye of the formula: ##STR30## 100 parts of the reaction product of polyethylene oxide of the molecular weight 300 with boric acid in the molar ratio 3:1, 30 parts of the diethanolamide of oleic acid and 840 parts of a 3% alginate thickening and the print is dried at 110° . It is then treated for five minutes at 185° C. with superheated steam and finished off as described in Example 2. A fast scarlet print on a white ground is obtained.

EXAMPLE 5

Cotton cloth is padded on a padding mangle with a solution containing 20 parts of the dye of the formula: ##STR31## 300 parts of a 3% alginate thickening, 550 parts of water and 130 parts of polyethylene oxide of the molecular weight 300. The cloth should take up 80% liquor. It is dried at 100° C. To fix the dye it is treated for five minutes with superheated steam at 190° C. The cloth is then rinsed cold, washed at 90° C. in a liquor containing 3 parts of the condensation product of a long chain alcohol with ethylene oxide to 997 parts of water.

A yellow dyeing is obtained.

Cloth of a blend of polyester and cotton in the ratio by weight 67:33 may be padded with the said solution instead of cotton cloth. A yellow dyeing is obtained in which the two phases are equal in tone. Fixation with hot air at 195° C. may also be carried out instead of the treatment with superheated steam.

EXAMPLE 6

Cotton cloth is padded on a padding mangle with a solution of 150 parts of polyethylene oxide in 850 parts of water so that the wet pickup is 80% and the padded cloth is dried at 100° C. The cloth treated in this way is printed by the rotary screen printing method with a color consisting of 30 parts of the dye of the formula: ##STR32## and 970 parts of a 10% alginate thickening. After the print has been dried at 105° C. it is treated for seven minutes at 185° C. with superheated steam and finished off by rinsing and soaping as described in Example 1.

A fast red print on a white ground is obtained.

The dyes specified in the following Examples may be converted as follows into a commercial dye formulation:

30 parts of dye,

6 parts of dispersing agent,

10 parts of a water retention agent,

1 part of a disinfectant and

about 53 parts of water

are ground in an agitator mill to a particle size of about 0.5 micron. A dispersion of the dye is thus obtained which is stable in storage.

EXAMPLE 7

20 Parts of 4-aminoazobenzene is stirred overnight with 80 parts by volume of 5 N hydrochloric acid. Then it is diluted with ice and water to a volume of 500 parts by volume at 10° C. 30 parts by volume of a 23% sodium nitrite solution is added and the whole is stirred for two hours at 15° C. The filtrate, in which excess nitrous acid has been removed in the conventional manner by adding sulfamic acid, is allowed to flow into a solution of 53 parts of 2,6-bis(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in 4000 parts by volume of dimethylformamide at 15° C. 150 parts by volume of a 50% aqueous sodium acetate solution is then added to this coupling mixture and the whole is stirred at 15° C. until coupling is completed. The dye formed is suction filtered, washed first with alcohol and then with hot water and dried at 90° C. A red powder is obtained which readily dissolves in dimethylformamide and polyethylene glycols with a yellowish red color and when printed in the form of these solutions or as an aqueous dispersion on cloth of polyester or cotton or a blend of the two types of fiber and aftertreated with hot air or superheated steam gives deep and clear scarlet hues.

EXAMPLE 8

35 parts of 3-chloro-4-aminoazobenzene is stirred overnight with 7 parts of an oxyethylated sperm oil alcohol containing about 23 ethylene oxide radicals and 120 parts by volume of 5 N hydrochloric acid. A volume of 750 parts by volume and a temperature of 10° C. are set up with ice and water and 450 parts by volume of a 23% aqueous sodium nitrite solution is introduced. After stirring for two hours at 15° C. a small amount of insoluble matter is filtered off and nitrous acid is removed in the usual way by adding an aqueous solution of sulfamic acid.

The diazonium salt solution thus obtained is then allowed to flow at 10° C. into 385 parts by volume of an isobutanol solution containing 0.16 mole of 2,6-bis-(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine. Complete coupling is achieved after stirring for several hours at 15° to 25° C. without adding the usual acid-binding agents. The dye formed is suction filtered, washed first with 100 parts by volume of isobutanol and then with 100 parts of hot water and then dried at 100° C.

The product which is in the form of a red powder may as an aqueous dispersion or dissolved in a polyethylene glycol be printed on cloth of polyester, cotton or a blend of both types of fiber and aftertreated with hot air or superheated steam. Deep and clear red hues of very good light and wet fastness properties are thus obtained.

EXAMPLE 9

The procedure described in Example 8 is adopted but the coupling component used is 0.15 mole of the substance having the formula: ##STR33## dissolved in 8000 parts by volume of dimethylformamide. The red powder obtained after isolation and drying dissolves in dimethylformamide and polyethylene glycols with a yellowish red color. Deep and clear scarlet hues with very good fastness properties are obtained on cloth of polyester, cotton or blends of the two.

Red hues having similar tinctorial properties are obtained in an analogous manner with the same diazo components and the following coupling components:

    __________________________________________________________________________      ##STR34##                                                                     Ex.                                                                               R.sup.1                R.sup.2                                              __________________________________________________________________________     10 H                                                                                                      ##STR35##                                           11                                                                                 ##STR36##               "                                                  12                                                                                 ##STR37##               "                                                  13                                                                                 ##STR38##               "                                                  14                                                                                 ##STR39##               "                                                  15   "                                                                                                    ##STR40##                                           16                                                                                 ##STR41##               "                                                  17                                                                                 ##STR42##               "                                                  18                                                                                 ##STR43##               "                                                  19                                                                                 ##STR44##                                                                                             ##STR45##                                           20                                                                                 ##STR46##                                                                                             ##STR47##                                           21                                                                                 ##STR48##                                                                                             ##STR49##                                           22 H                        "                                                  __________________________________________________________________________

example 23

16 parts of o-trifluoromethylaniline is dissolved in 30 parts by volume of 10 N hydrochloric acid and 200 parts of water, 200 parts of ice is added and then 30 parts by volume of a 23% aqueous solution of sodium nitrite is allowed to flow in below the surface. After stirring for half an hour at 0° to 5° C. the excess of nitrous acid is destroyed as usual by adding an aqueous solution of sulfamic acid.

The solution of the diazonium salt thus obtained is gradually added at 5° to 10° C. to a solution of 54 parts of bis-(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in 1000 parts by volume of dimethylformamide and then 32 parts by volume of a 50% aqueous sodium acetate solution is added. When coupling is over the yellow dye formed is suction filtered, washed first with alcohol and then with hot water and dried at 100° C. The yellow powder thus obtained dissolves in dimethylformamide or polyglycols with a pure yellow color and when printed on to cloth of cotton, polyester or blends of both and fixed gives deep and clear yellow hues with very good fastness properties.

The following dyes are obtained in a similar manner with the same coupling components:

    ______________________________________                                                                     Hue on cotton                                      Ex.  Diazo Component        and polyester                                      ______________________________________                                         24   m-trifluoromethylaniline                                                                              yellow                                             25   4-chloro-2-trifluoromethylaniline                                                                     "                                                  26   2-cyanoaniline         "                                                  27   4-chloro-2-cyanoaniline                                                                               "                                                  28   2,4-dicyanoaniline     yellowish orange                                   29   2-chloroaniline-4-methylsulfone                                                                       reddish yellow                                     30   2-aminodiphenylsulfone reddish yellow                                     31   3-aminophthalic hydroxyethylimide                                                                     yellowish orange                                   ______________________________________                                    

EXAMPLE 32

25.3 Parts of the p-tolylimide of 3-aminophthalic acid is introduced at 15° to 25° C. into 60 parts of 96% sulfuric acid while stirring. The mixture is further stirred at the same temperature until complete solution has taken place. Then 32 parts (0.1 mole) of nitrosylsulfuric acid is allowed to flow in slowly at 0° to 5° C. and the diazotization mixture is stirred for another thirty minutes at 0° to 5° C. and then introduced into a mixture of 125 parts of ice and 25 parts of ice-water.

After the excess of nitrite has been destroyed with sulfamic acid the diazonium salt is stirred while 300 parts by volume of isobutanol and 110 parts by volume of a 10-molar solution of 2,6-bis(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in isobutanol are introduced. After coupling is over the dye formed is suction filtered, washed first with isobutanol and then with hot water and dried at 100° C. The reddish powder thus obtained dissolves in polyglycols with a reddish yellow color and gives deep orange hues with very good fastness properties on polyester, cotton or blends of the two after having been printed and fixed.

The following dyes may be obtained by similar methods with the same coupling components:

    ______________________________________                                                                       Hue on                                                                         polyester                                        Ex.  Diazo components         and cotton                                       ______________________________________                                         33   1-aminoanthraquinone     brown                                            34   1-aminoanthraquinone-6-carboxylic acid                                                                  brown                                            35   1-amino-2-chloroanthraquinone                                                                           brown                                            36   1-amino-2-bromoanthraquinone                                                                            brown                                            37   1-amino-2,4-dichloroanthraquinone                                                                       brown                                            38   4-amino-3-methoxybenzanthrone                                                                           brown                                            39   2-aminoanthraquinone     red                                              40   2-amino-3-chloroanthraquinone                                                                           red                                              41   2-amino-1-chloroanthraquinone                                                                           red                                              42   2-amino-2-cyano-3-bromoanthraquinone                                                                    red                                              43   2-amino-3-bromoanthraquinone                                                                            red                                              44   1-aminobenzanthrone      reddish violet                                   45   5-nitro-3-aminobenzoisothiazole-(2,3)                                                                   bluish violet                                    46   5-nitro-2-aminothiazole  reddish violet                                   ______________________________________                                    

The following dyes are obtainable according to the processes of the foregoing Examples:

    __________________________________________________________________________     Ex.                                                                              Diazo components             Coupling components         Hue                 __________________________________________________________________________     47                                                                                ##STR50##                                                                                                   ##STR51##                  scarlet             48                                                                                ##STR52##                   "                           red                 49                                                                                ##STR53##                   "                           ruby                50                                                                                ##STR54##                   "                           reddish                                                                        violet              51                                                                                ##STR55##                                                                                                   ##STR56##                  red                 52                                                                                ##STR57##                   "                           red                 53                                                                                ##STR58##                   "                           orange              54                                                                                ##STR59##                                                                                                   ##STR60##                  reddish                                                                        orange              55                                                                                ##STR61##                   "                           reddish                                                                        orange              56                                                                                ##STR62##                   "                           scarlet             57                                                                                ##STR63##                   "                           yel- lowish                                                                    orange              58                                                                                ##STR64##                   "                           red                  ##STR65##                                                                     Ex.                                                                            No.                                                                               D                  X    R.sup.1                                                                            R.sup.2    Hue                                  __________________________________________________________________________     59                                                                                 ##STR66##         CN   H   (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          red                                  60 "                  CN   C.sub.2 H.sub.5                                                                    "          red                                  61 "                  CN   C.sub.3 H.sub.7(n)                                                                 "          red                                  62                                                                                 ##STR67##         CN   C.sub.6 H.sub.5                                                                    "          golden yellow                        63 "                  CONH.sub.2                                                                          H   (CH.sub.2).sub.3 OCH.sub.3                                                                orange                               64                                                                                 ##STR68##         "    H   "          scarlet                              65                                                                                 ##STR69##         "    H   "          red                                  66                                                                                 ##STR70##         CN   CH.sub.3                                                                           "          red                                  67 "                  CONH.sub.2                                                                          H   "          red                                  68                                                                                 ##STR71##         CN   CH.sub.3                                                                           (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          red                                  69 "                  CN   H   "          red                                  70 "                  CN   CH.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                               red                                  71 "                  CONH.sub.2                                                                          H   "          bluish                                                                         red                                  72                                                                                 ##STR72##         CN   CH.sub.3                                                                           (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          bluish red                            ##STR73##                                                                     Ex. No.                                                                             D                          Hue                                            __________________________________________________________________________     73                                                                                   ##STR74##                 scarlet                                        74                                                                                   ##STR75##                 scarlet                                        75                                                                                   ##STR76##                 scarlet                                        76                                                                                   ##STR77##                 red                                            77                                                                                   ##STR78##                 red                                            78                                                                                   ##STR79##                 red                                            79                                                                                   ##STR80##                 red                                            80                                                                                   ##STR81##                 red                                            81                                                                                   ##STR82##                 red                                            82                                                                                   ##STR83##                 orange                                         83                                                                                   ##STR84##                 orange                                          ##STR85##                                                                     Ex. No.                                                                             D                          Hue                                            __________________________________________________________________________     84                                                                                   ##STR86##                 golden yellow                                  85                                                                                   ##STR87##                 golden yellow                                  86                                                                                   ##STR88##                 orange                                         87                                                                                   ##STR89##                 orange                                         88                                                                                   ##STR90##                 ruby                                            ##STR91##                                                                     Ex. No.                                                                             D                          Hue                                            __________________________________________________________________________     89                                                                                   ##STR92##                 scarlet                                        90                                                                                   ##STR93##                 red                                            91                                                                                   ##STR94##                 red                                            92                                                                                   ##STR95##                 red                                            93                                                                                   ##STR96##                 red                                            94                                                                                   ##STR97##                 red                                            95                                                                                   ##STR98##                 red                                            96                                                                                   ##STR99##                 red                                            97                                                                                   ##STR100##                red                                            98                                                                                   ##STR101##                red                                            99                                                                                   ##STR102##                orange                                         100                                                                                  ##STR103##                golden yellow                                  101                                                                                  ##STR104##                orange                                         102                                                                                  ##STR105##                orange                                          ##STR106##                                                                    Ex. No.                                                                             D                  R        Hue                                           __________________________________________________________________________     103                                                                                  ##STR107##        H        reddish orange                                104  "                  CH.sub.3 reddish                                                                        orange                                        105  "                  COC.sub.6 H.sub.5                                                                       reddish                                                                        orange                                        106                                                                                  ##STR108##        "        golden yellow                                 107                                                                                  ##STR109##        "        golden yellow                                 108                                                                                  ##STR110##        "        reddish orange                                109  "                  H        reddish                                                                        orange                                        110                                                                                  ##STR111##        H        red                                           111                                                                                  ##STR112##        COC.sub.6 H.sub.5                                                                       red                                           112  "                                                                                                  ##STR113##                                                                             red                                           113  "                  CH.sub.3 red                                           114  "                  C.sub.2 H.sub.5                                                                         red                                           115                                                                                  ##STR114##        "        red                                           116  "                  CH.sub.3 red                                           117  "                  H        red                                           118                                                                                  ##STR115##        H        yellowish orange                              119  "                  CH.sub.3 yellowish                                                                      orange                                        120  "                  C.sub.2 H.sub.5                                                                         yellowish                                                                      orange                                        121                                                                                  ##STR116##        C.sub.2 H.sub.5                                                                         red                                           122  "                  CH.sub.3 red                                           123  "                  H        red                                            ##STR117##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     124                                                                                  ##STR118##        golden yellow                                          125                                                                                  ##STR119##        orange                                                 126                                                                                  ##STR120##        golden yellow                                          127                                                                                  ##STR121##        reddish orange                                         128                                                                                  ##STR122##        red                                                    129                                                                                  ##STR123##        red                                                    130                                                                                  ##STR124##        reddish orange                                         131                                                                                  ##STR125##        reddish orange                                         132                                                                                  ##STR126##        red                                                    133                                                                                  ##STR127##        red                                                    134                                                                                  ##STR128##        orange                                                 135                                                                                  ##STR129##        orange                                                  ##STR130##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     136                                                                                  ##STR131##        bluish red                                             137                                                                                  ##STR132##        bluish red                                             138                                                                                  ##STR133##        Bordeaux                                               139                                                                                  ##STR134##        Bordeaux                                               140                                                                                  ##STR135##        bluish red                                             141                                                                                  ##STR136##        orange                                                 142                                                                                  ##STR137##        orange                                                  ##STR138##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     143                                                                                  ##STR139##        reddish orange                                         144                                                                                  ##STR140##        red                                                    145                                                                                  ##STR141##        red                                                    146                                                                                  ##STR142##        red                                                    147                                                                                  ##STR143##        red                                                    148                                                                                  ##STR144##        reddish orange                                         149                                                                                  ##STR145##        reddish orange                                         150                                                                                  ##STR146##        golden yellow                                          151                                                                                  ##STR147##        golden yellow                                          152                                                                                  ##STR148##        golden yellow                                          153                                                                                  ##STR149##        golden yellow                                           ##STR150##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     154                                                                                  ##STR151##        reddish orange                                         155                                                                                  ##STR152##        red                                                    156                                                                                  ##STR153##        red                                                    157                                                                                  ##STR154##        red                                                    158                                                                                  ##STR155##        red                                                    159                                                                                  ##STR156##        orange                                                 160                                                                                  ##STR157##        orange                                                 161                                                                                  ##STR158##        golden yellow                                          162                                                                                  ##STR159##        golden yellow                                          163                                                                                  ##STR160##        golden yellow                                          164                                                                                  ##STR161##        golden yellow                                           ##STR162##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     165                                                                                  ##STR163##        reddish  orange                                        166                                                                                  ##STR164##        red                                                    167                                                                                  ##STR165##        red                                                    168                                                                                  ##STR166##        red                                                    169                                                                                  ##STR167##        red                                                    170                                                                                  ##STR168##        reddish orange                                         171                                                                                  ##STR169##        reddish orange                                         172                                                                                  ##STR170##        golden yellow                                          173                                                                                  ##STR171##        golden  yellow                                         174                                                                                  ##STR172##        golden yellow                                          175                                                                                  ##STR173##        golden yellow                                           ##STR174##                                                                    Ex. No.                                                                             D                  Hue                                                    __________________________________________________________________________     176                                                                                  ##STR175##        reddish orange                                         177                                                                                  ##STR176##        red                                                    178                                                                                  ##STR177##        red                                                    179                                                                                  ##STR178##        red                                                    180                                                                                  ##STR179##        red                                                    181                                                                                  ##STR180##        reddish orange                                         182                                                                                  ##STR181##        reddish orange                                         183                                                                                  ##STR182##        golden yellow                                          184                                                                                  ##STR183##        golden yellow                                          185                                                                                  ##STR184##        golden yellow                                          186                                                                                  ##STR185##        golden yellow                                           ##STR186##                                                                    Ex.                                                                            No.                                                                               R.sup.1            R.sup.2      Hue                                         __________________________________________________________________________     187                                                                                ##STR187##                                                                                        ##STR188##  yellow                                      188                                                                                ##STR189##        "            yellow                                      189                                                                               NH.sub.2           "            yellow                                      190                                                                                ##STR190##                                                                                        ##STR191##  yellow                                      191                                                                               "                                                                                                  ##STR192##  yellow                                      192                                                                               "                                                                                                  ##STR193##  yellow                                       ##STR194##                                                                    __________________________________________________________________________     193                                                                               NH.sub.2                                                                                           ##STR195##  yellow                                      Coupling components   Diazo component                                           ##STR196##                                                                                           ##STR197##                                              __________________________________________________________________________     194                                                                                ##STR198##                                                                                        ##STR199##  yellow                                       ##STR200##                                                                                           ##STR201##                                              __________________________________________________________________________     195                                                                                ##STR202##                                                                                        ##STR203##  golden yellow                               196                                                                                ##STR204##                                                                                        ##STR205##  orange                                      197                                                                               "                                                                                                  ##STR206##  orange                                      198                                                                               "                                                                                                  ##STR207##  orange                                      Coupling components   Diazo component                                           ##STR208##                                                                                           ##STR209##                                              __________________________________________________________________________     199                                                                                ##STR210##                                                                                        ##STR211##  golden yellow                               200                                                                                ##STR212##                                                                                        ##STR213##  orange                                      201                                                                               "                                                                                                  ##STR214##  orange                                      Coupling components   Diazo component                                           ##STR215##                                                                                           ##STR216##                                              __________________________________________________________________________     202                                                                                ##STR217##                                                                                        ##STR218##  golden yellow                               203                                                                               NH.sub.2           "            orange                                      204                                                                                ##STR219##                                                                                        ##STR220##  orange                                      205                                                                               "                                                                                                  ##STR221##  orange                                      206                                                                               "                                                                                                  ##STR222##  orange                                      207                                                                               "                                                                                                  ##STR223##  golden yellow                               208                                                                               "                                                                                                  ##STR224##  golden yellow                               Coupling components   Diazo component                                           ##STR225##                                                                                           ##STR226##                                              __________________________________________________________________________     209                                                                                ##STR227##                                                                                        ##STR228##  orange                                      210                                                                               "                                                                                                  ##STR229##  orange                                      211                                                                               "                                                                                                  ##STR230##  orange                                      212                                                                               "                                                                                                  ##STR231##  orange                                      213                                                                               "                                                                                                  ##STR232##  orange                                      Coupling components   Diazo component                                           ##STR233##                                                                                           ##STR234##                                              __________________________________________________________________________     214                                                                                ##STR235##                                                                                        ##STR236##  reddish  orange                             215                                                                                ##STR237##                                                                                        ##STR238##  "                                           216                                                                                ##STR239##                                                                                        ##STR240##  "                                           217                                                                               "                                                                                                  ##STR241##  red                                         218                                                                               "                                                                                                  ##STR242##  "                                           219                                                                               NH.sub.2                                                                                           ##STR243##  orange                                      Coupling Components   Diazo component                                           ##STR244##                                                                    __________________________________________________________________________     220                                                                                ##STR245##                                                                                        ##STR246##  red                                         221                                                                                ##STR247##        "            "                                           222                                                                               "                                                                                                  ##STR248##  "                                           223                                                                               NH.sub.2                                                                                           ##STR249##  "                                           224                                                                                ##STR250##                                                                                        ##STR251##  "                                           225                                                                               "                                                                                                  ##STR252##  "                                           226                                                                               "                                                                                                  ##STR253##  "                                           227                                                                               "                                                                                                  ##STR254##  "                                           Coupling components   Diazo component                                           ##STR255##                                                                    __________________________________________________________________________     228                                                                                ##STR256##                                                                                        ##STR257##   violetBluish                               229                                                                               "                                                                                                  ##STR258##  "                                           230                                                                                ##STR259##        "            "                                           231                                                                               NH.sub.2           "            violet                                      232                                                                                ##STR260##                                                                                        ##STR261##   violetbluish                               233                                                                               "                                                                                                  ##STR262##  blue                                        234                                                                               "                  N            "                                           235                                                                               "                  N            "                                           Ex. No. 236                                                                           ##STR263##                    red                                        ##STR264##                                                                    Ex.                                                                            No.                                                                               R.sup.1                     R.sup.2                                                                           R.sup.3                                                                           R.sup.4    R.sup.5    Hue                 __________________________________________________________________________     237                                                                                ##STR265##                 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.2 CH.sub.2 OCH.sub.3                                                               CH.sub.2 CH.sub.2                                                              OCH.sub.3  red                 238                                                                               "                           "  "  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                      CH.sub.2 CH.sub.2                                                              CH.sub.2 OCH.sub.3                                                                        "                   239                                                                               "                           "  "  "          C.sub.6 H.sub.5                                                                           "                   240                                                                                ##STR266##                 "  "  "          "          "                   241                                                                                ##STR267##                 "  "  "          "          "                   242                                                                               "                           "  "  "          CH.sub.2 CH.sub.2                                                              CH.sub.2 OCH.sub.3                                                                        "                   243                                                                               "                           H  "  "          "          "                   244                                                                               "                           Cl H  "          "          "                   245                                                                                ##STR268##                 CH.sub.3                                                                          CH.sub.3                                                                          "          C.sub.6 H.sub.5                                                                           "                   246                                                                               "                           "  "  "          (CH.sub.2).sub.3 O(CH.sub.                                                     2).sub.2 OC.sub.6                                                                         ".sub.5             247                                                                                ##STR269##                 "  "  "          "          "                   248                                                                                ##STR270##                 "  "  (CH.sub.2).sub.3 O(CH.sub.2 O(C.sub.6                                           H.sub.5   "          "                   249                                                                                ##STR271##                 "  "  "          "          "                   250                                                                                ##STR272##                 "  "  "          "          "                   251                                                                               "                           "  "  (CH.sub.2).sub.3 OCH.sub.3                                                                "          "                   252                                                                               H                           Cl H  (CH.sub.2).sub.5COOH                                                                      "          "                   253                                                                               HOOC                        CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          "          "                   254                                                                               H                           H  H  (CH.sub.2).sub.5COOH                                                                      "          orange              255                                                                               H                           CH.sub.3                                                                          CH.sub.3                                                                          "          "          "                   256                                                                               H                           Cl H  (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          COCH.sub.3 scarlet             257                                                                               "                           "  "  "          SO.sub.2 CH.sub.3                                                                         "                   Coupling component                                                              ##STR273##                                                                       Diazo components    Hue                                                     __________________________________________________________________________     258                                                                                ##STR274##         yellow                                                  259                                                                                ##STR275##         orange                                                  260                                                                                ##STR276##         "                                                       261                                                                                ##STR277##         scarlet                                                 262                                                                                ##STR278##         "                                                       263                                                                                ##STR279##         "                                                       264                                                                                ##STR280##         bluish red                                              265                                                                                ##STR281##         "                                                       266                                                                                ##STR282##         reddish violet                                          267                                                                                ##STR283##         "                                                       268                                                                                ##STR284##         ruby                                                    269                                                                               trichloroaniline    yellow                                                  270                                                                               tribromoaniline     yellow                                                  Coupling component                                                              ##STR285##                                                                    Ex.                                                                               Diazo components                                                                             R  X   R.sup.3    Hue                                         __________________________________________________________________________     271                                                                               1-aminoanthraquinone                                                                         CH.sub.3                                                                          CN  H          brown                                       272                                                                               "             H  CN  H          brown                                       273                                                                               "             H  CONH.sub.2                                                                         H          reddish brown                               274                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.5                                                                           brown                                       275                                                                               "             H  CN  C.sub.6 H.sub.5                                                                           brown                                       276                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           reddish brown                               277                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.4 CH.sub.3 (p)                                                              brown                                       278                                                                               1-amino-2-chloroanthra-                                                                      CH.sub.3                                                                          CN  H          brown                                          quinone                                                                     279                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.5                                                                           brown                                       280                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.4 CH.sub.3 (p                                                               brown                                       281                                                                               "             H  CN  C.sub.6 H.sub.5                                                                           brown                                       282                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           reddish brown                               283                                                                               1-amino-2-methylanthraquin-                                                                  CH.sub.3                                                                          CN  H          brown                                          one                                                                         284                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.5                                                                           brown                                       285                                                                               3-amino-5-nitro-benzoiso-                                                                    H  CN  H          violet                                         thiazole-(2,1)                                                              286                                                                               "             H  CONH.sub.2                                                                         H          navy blue                                   287                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           blue                                        288                                                                               3-amino-5-nitro-7-bromo-                                                                     H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           blue                                           benzoisothiazole-(2,1)                                                      289                                                                               "             H  CONH.sub.2                                                                         H          navy blue                                   290                                                                               "             H  CN  H          bluish violet                               291                                                                                ##STR286##   CH.sub.3                                                                          CN  H          orange                                      292                                                                               "             CH.sub.3                                                                          CN  C.sub.6 H.sub.5                                                                           orange                                      293                                                                               "             H  CN  H          orange                                      294                                                                               "             H  CONH.sub.2                                                                         H          scarlet                                     295                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           scarlet                                     296                                                                                ##STR287##   CH.sub.3                                                                          CN  C.sub.6 H.sub.5                                                                           orange                                      297                                                                               "             H  CN  C.sub.6 H.sub.5                                                                           orange                                      298                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           scarlet                                     299                                                                               "             H  CONH.sub.2                                                                         H          orange                                      300                                                                                ##STR288##   H  CN  H          red                                         301                                                                               "             H  CN  C.sub.6 H.sub.5                                                                           red                                         302                                                                               "             H  CONH.sub.2                                                                         C.sub.6 H.sub.5                                                                           ruby                                        303                                                                               "             H  CONH.sub.2                                                                         H          ruby                                        304                                                                               "             H  CN  (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    red                                         305                                                                                ##STR289##   H  CONH.sub.2                                                                         H          ruby                                        306                                                                               "             H  CN  H          red                                         307                                                                               "             H  CN  C.sub.6 H.sub.5                                                                           red                                         308                                                                               "             CH.sub.3                                                                          CN  (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6                                                red                                         309                                                                                ##STR290##   CH.sub.3                                                                          CN  H          orange                                      310                                                                               "             H  CN  H          orange                                      311                                                                               "             H  CONH.sub.2                                                                         H          scarlet                                     Coupling components                                                             ##STR291##                                                                    Ex.                                                                               Diazo components                                                                             R.sup.3                                                                               Z          Hue                                         __________________________________________________________________________     312                                                                                ##STR292##   H      (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    orange                                      313                                                                               "             C.sub.6 H.sub.5                                                                       "          orange                                      314                                                                                ##STR293##   H      "          orange                                      315                                                                                ##STR294##   H      "          orange                                      316                                                                                ##STR295##   H      "          scarlet                                     317                                                                                ##STR296##   H      "          scarlet                                     318                                                                               3-aminophthalic p-tolyl-                                                                     H      "          red                                            imide                                                                       319                                                                               1-aminoanthraquinine                                                                         H      "          reddish brown                               320                                                                               aminoazobenzene                                                                              H      "          ruby                                        321                                                                               chloroaminoazobenzene                                                                        H      "          reddish violet                              322                                                                               bromoaminoazobenzene                                                                         H      "          reddish violet                              323                                                                               3-amino-5-nitrobenziso-                                                                      H      "          navy blue                                      thiazole-(2,1)                                                              324                                                                               "             C.sub.6 H.sub.5                                                                       "          navy blue                                   325                                                                               "             C.sub.6 H.sub.4 CH.sub.3 (p)                                                          "          navy blue                                   326                                                                               3-amino-5-nitro-7-bromo-                                                                     H      "          navy blue                                      benzoisothiazole-(2,1)                                                      327                                                                               "             C.sub.6 H.sub.5                                                                       "          navy blue                                   328                                                                               4-aminoazobenzene                                                                            H      H          orange                                      329                                                                               4-amino-3-chloroazobenzene                                                                   H      H          scarlet                                     The following are also suitable as dyes:                                       Example                                        Hue                             __________________________________________________________________________     330                                                                                  ##STR297##                               orange                          331                                                                                  ##STR298##                               yellow                          332                                                                                  ##STR299##                               brown                           333                                                                                  ##STR300##                               red                                   ##STR301##                                                               Example                                                                             R                                         Hue                             __________________________________________________________________________     334  C.sub.6 H.sub.5                           red                             335  C.sub.6 H.sub.4 CH.sub.3 (o)              red                             336  C.sub.6 H.sub.4 CH.sub.3 (p)              red                             337                                                                                  ##STR302##                               red                              ##STR303##                                                                    Example                                                                               D                      R.sup.1       R.sup.3      Hue                   __________________________________________________________________________     338                                                                                    ##STR304##            (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5       (CH.sub.2).sub.3 (CH.sub.2).su                                                 b.2 OC.sub.6 H.sub.5                                                                        orange                339                                                                                    ##STR305##            "             "            orange                340                                                                                    ##STR306##            "                                                                                             ##STR307##  orange                341    "                      "                                                                                             ##STR308##  orange                342    "                      "             (CH.sub.2).sub.2C.sub.6                                                        H.sub.5      orange                343    "                                                                                                      ##STR309##   (CH.sub.2).sub.3 O(CH.sub.2).s                                                 ub.2 OC.sub.6 H.sub.5                                                                       orange                344                                                                                    ##STR310##            (CH.sub.2).sub.2 OCH.sub.3                                                                   (CH.sub.2).sub.2 OCH.sub.3                                                                  orange                345    "                      (CH.sub.2).sub.3 OCH.sub.3                                                                   (CH.sub.2).sub.                                                                             orangesub.3           346    "                      (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5       (CH.sub.2).sub.3 O(CH.sub.2).s                                                 ub.2 OC.sub.6 H.sub.5                                                                       orange                347                                                                                    ##STR311##            (CH.sub.2).sub.2 OCH.sub.3                                                                   (CH.sub.2).sub.2 OCH.sub.3                                                                  orange                348    "                      (CH.sub.2).sub.3 OCH.sub.3                                                                   (CH.sub.2).sub.3 OCH.sub.3                                                                  orange                349    "                      (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5       (CH.sub.2).sub.3 O(CH.sub.2).s                                                 ub.2 OC.sub.6 H.sub.5                                                                       orange                Example                                                                              D                      R.sup.1       R.sup.2       Hue                   __________________________________________________________________________     350                                                                                   ##STR312##            (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5       (CH.sub.2).sub.3 O(CH.sub.2).su                                                b.2 OC.sub.6 H.sub.5                                                                         orange                351                                                                                   ##STR313##            "             "             orange                352                                                                                   ##STR314##            "             "             orange                353                                                                                   ##STR315##            "             "             orange                354                                                                                   ##STR316##            "             "             orange                355                                                                                   ##STR317##            "             "             orange                356                                                                                   ##STR318##            "             "             orange                357                                                                                   ##STR319##            "             "             orange                358                                                                                   ##STR320##            "             "             orange                359   "                      NH.sub.2      "             orange                360   "                      (CH.sub.2).sub.2 OCH.sub.3                                                                   (CH.sub.2).sub.2 OCH.sub.3                                                                   orange                361   "                      (CH.sub.2).sub.3 OCH.sub.3                                                                   (CH.sub.2).sub.3 OCH.sub.3                                                                   orange                Example                                                                             D                    R.sup.1    R.sup.3    Hue                            __________________________________________________________________________     362                                                                                  ##STR321##          (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4                                    H.sub.9    (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.4 H.sub.9                                                                          red                            363                                                                                  ##STR322##          "          "          brown                          364                                                                                  ##STR323##          "          "          orange                         365                                                                                  ##STR324##          "          "          orange                         366                                                                                  ##STR325##          "          "          orange                         367                                                                                  ##STR326##          "          "          orange                          ##STR327##                                                                    Exam-                                                                          ple T.sup.3         T.sup.4                                                                          T.sup.5       R.sup.3     R.sup.1     Hue                __________________________________________________________________________     368 SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                 H H             (CH.sub.2).sub.2 OCH.sub.3                                                                 (CH.sub.2).sub.2 OCH.sub.3                                                                 red                369 "                 "             (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                 red                370 "                 "             (CH.sub.2).sub.3 O(CH.sub. 2).sub.2                                            OC.sub.6 H.sub.5                                                                           (CH.sub.2).sub.3 O(CH.sub.                                                     2).sub.2 OC.sub.6                                                                          redub.5            371 "                 "             (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                           (CH.sub.2).sub.3 O(CH.sub.                                                     2).sub.2 OC.sub.6                                                                          redub.5            372 "               Cl                                                                               "             "           "           red                373 "               Cl                                                                               "             (CH.sub.2).sub.2 OCH.sub.3                                                                 (CH.sub.2).sub.2 OCH.sub.3                                                                 red                374 "               Cl                                                                               "             (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                 red                375 CONH(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                        H "             "           "           red                376 "               H "             (CH.sub.2).sub.2 OCH.sub.3                                                                 (CH.sub.2).sub.2 OCH.sub.3                                                                 red                377 "               H "             (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                           (CH.sub.2).sub.3 O(CH.sub.                                                     2).sub.2 OC.sub.6                                                                          redub.5            378 Cl              Cl                                                                               SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4                                   OC.sub.6 H.sub.5                      red                 ##STR328##                                                                    Example                                                                             R.sup.1            Hue                                                    __________________________________________________________________________     379                                                                                  ##STR329##        bluish violet                                          380                                                                                  ##STR330##        blue                                                   381                                                                                  ##STR331##        blue                                                   382  (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9                                               bluish violet                                          383                                                                                  ##STR332##        blue                                                    ##STR333##                                                                    Example                                                                             D               R  X    Hue                                               __________________________________________________________________________     384                                                                                  ##STR334##     CH.sub.3                                                                          CN   scarlet                                           385  "               H  CN   scarlet                                           386  "               H  CONH.sub.2                                                                          red                                               387                                                                                  ##STR335##     CH.sub.3                                                                          CN   red                                               388  "               H  CN   red                                               389  "               H  CONH.sub.2                                                                          ruby                                              390                                                                                  ##STR336##     CH.sub.3                                                                          CN   yellow                                            391  "               H  CONH.sub.2                                                                          orange                                            392                                                                                  ##STR337##     CH.sub.3                                                                          CN   yellowish orange                                  393  "               H  CONH.sub.2                                                                          reddish orange                                    394                                                                                  ##STR338##     CH.sub.3                                                                          CN   orange                                            395  "               H  CONH.sub.2                                                                          scarlet                                            ##STR339##                                                                    No.                                                                               T.sup.4                                                                           T.sup.3      T.sup.1                                                                           T.sup.2                                                                           R.sup.3                                                                               R.sup.1                                                                               shade                                   __________________________________________________________________________     396                                                                               H  H            H  H  C.sub.4 H.sub.9 (n)                                                                   C.sub.4 H.sub.9 (n)                                                                   orange                                  397                                                                               4-Cl                                                                              H            CH.sub.3                                                                          H  C.sub.3 H.sub.7 (n)                                                                   C.sub.3 H.sub.7 (n)                                                                   red                                     398                                                                               4-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     399                                                                               4-Cl                                                                              H            CH.sub.3                                                                          H  "      "      red                                     400                                                                               2-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          "      "      red                                     401                                                                               4-Cl                                                                              H            CH.sub.3                                                                          H  C.sub.4 H.sub.9 (n)                                                                   C.sub.4 H.sub.9 (n)                                                                   red                                     402                                                                               H  H            Br H  "      "      red                                     403                                                                               3-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2 ).sub.3 OCH.sub.3                                                           (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     404                                                                               3-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     405                                                                               4-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          "      "      red                                     406                                                                               4-Cl                                                                              H            CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     407                                                                               4-Cl                                                                              H            CH.sub.3                                                                          H  "      "      red                                     408                                                                               4-Cl                                                                              H            CH.sub.3                                                                          H  (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     409                                                                               H  H            Cl H  C.sub.4 H.sub.9 (n)                                                                   C.sub.4 H.sub.9 (n)                                                                   red                                     410                                                                               2-Cl                                                                              H            CH.sub.3                                                                          H  C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     411                                                                               2-Cl                                                                              H            CH.sub.3                                                                          H  (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     412                                                                               2-Cl                                                                              H            CH.sub.3                                                                          H  (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     413                                                                               3-Cl                                                                              H            CH.sub.3                                                                          H  (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     414                                                                               H  3-CONHC.sub.2 H.sub.4 OCH.sub.3                                                             CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             red                                     415                                                                               H  "            CH.sub.3                                                                          CH.sub.3                                                                          "      "      red                                     416                                                                               H  3-CONH(CH).sub.3 OCH.sub.3                                                                  CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     417                                                                               H  4-C.sub.6 H.sub.5 O(CH.sub.2).sub.3 NHCO                                                    "  CH.sub.3                                                                          H      C.sub.4 H.sub.9                                                                       red                                     418                                                                               H  4-C.sub.2 H.sub.5 O.sub.2 C                                                                 CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       dark                                                                           red                                     419                                                                               H  4-C.sub.2 H.sub.5 O.sub.2 C                                                                 CH.sub.3                                                                          CH.sub.3                                                                          H      C.sub.4 H.sub.9                                                                       red                                     420                                                                               H  4-CH.sub.3 O(CH.sub.2).sub.2 NHCO                                                           CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     421                                                                               H  4-C.sub.2 H.sub.5 O.sub.2 C                                                                 CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.2 OCH.sub.3                                                            "      dark                                                                           red                                     422                                                                               H  "            CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            "                                       423                                                                               H  4-CH.sub.3 O(CH.sub.2).sub.2 NHCO                                                           CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     424                                                                               H  4-C.sub.3 H.sub.7 (n)O.sub.2 C                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     425                                                                               H  4-C.sub.3 H.sub.7 (i)O.sub.2 C                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     426                                                                               H  3-CONHC.sub.3 H.sub.7 (n)                                                                   "  "  (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     427                                                                               H  4-CONHC.sub.3 H.sub.7 (n)                                                                   "  "  "      "      red                                     428                                                                               H  4-SO.sub.2 NHC.sub.4 H.sub.9 (n)                                                            "  "  C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     429                                                                               H  "            "  "  C.sub.3 H.sub.17                                                                      C.sub.3 H.sub.17                                                                      red                                     430                                                                               H  "            "  "  (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     431                                                                               H  4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                         "  "  C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       red                                     432                                                                               H  "            "  "  (CH.sub.2).sub. 2 OCH.sub.3                                                           (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     433                                                                               H  "            "  "  (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                            red                                     434                                                                               H  H            "  "  H      H      red                                     435                                                                               H  H            Cl "  (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                            red                                     436                                                                               H  H            Br "  "      "      red                                     437                                                                               H  H            H  "  "      "      red                                     438                                                                               H                                                                                  ##STR340##  H  "  "      "      red                                     439                                                                               H                                                                                  ##STR341##  H  "  "      "      red                                     440                                                                               H  "            CH.sub.3                                                                          CH.sub.3                                                                          "      "      red                                     __________________________________________________________________________ 

We claim:
 1. Uniformly dyed water-swellable cellulosic fibers, said fibers being fast to washing, dry cleaning, sublimation and light and having been produced by contacting water-swellable cellulose fibers subsequently or concomitantly with water, ethylene glycol or a derivative thereof and, while the fibers are still swollen, an essentially water-insoluble dye of the formula ##STR342## in which D is phenyl substituted by cyano, trifluoromethyl, methyl, fluoro, chloro, bromo, C₁ to C₄ alkylsulfonyl, phenylsulfonyl, ##STR343## anthraquinonyl; anthraquinonyl substituted by methyl, chloro, bromo or carboxyl; or benzoisothiazolyl substituted by nitro, chloro or bromo;R is hydrogen, C₁ to C₃ alkyl or phenyl; X is cyano, carbamoyl or ##STR344## R¹ and R³ independently of one another are hydrogen; C₁ to C₈ alkyl; C₂ to C₈ alkyl substituted by hydroxy, C₁ to C₈ alkoxy, phenoxy, tolyloxy, cyclohexyloxy, benzyloxy, β-phenylethoxy, carboxyl, carboxylic ester with a total of 2 to 9 carbon atoms, carboxylic acyloxy with a total of 1 to 11 carbon atoms, C₁ to C₈ alkylaminocarbonyloxy, benzoylaminocarbonyloxy, tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy, dichlorophenylaminocarbonyloxy or pyrrolidonyl; cyclohexyl, norbornyl; phenyl-C₁ to C₄ -alkyl; tolyl-C₁ to C₄ -alkyl; β-phenyl-β-hydroxy-ethyl; phenyl; phenyl substituted by fluoro, chloro, bromo, methyl, trifluoromethyl, ethyl, methoxy, ethoxy or pyrrolidonyl; CH₂ CH₂ OCH₂ CH₂ OH; or (CH₂)₃ (OC₂ H₄)_(n) OB; n is zero, 1 or 2; B is hydrogen, C₁ to C₄ alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or tolyl; R² and R⁴ independently of one another are hydrogen or C₁ to C₄ alkyl; R¹ to R² together with the nitrogen are pyrrolidino, piperidino, morpholino or hexamethyleneimino; T¹ is hydrogen, chloro, bromo or methyl; T² is hydrogen or methyl; T³ is hydrogen, ##STR345## or COOB¹ ; B¹ is hydrogen, C₁ to C₈ alkyl, phenyl-C₁ to C₄ -alkyl or (OC₂ H₄)_(n) OB; Y is --SO₂ -- or --CO--; T⁴ is hydrogen or chloro; and T⁵ is hydrogen, methyl or ethyl.
 2. The fibers according to claim 1 wherein in the formula D is phenyl-substituted cyano, trifluoromethyl, fluoro, chloro, bromo, methylsulfonyl, phenylsulfonyl or ##STR346## anthraquinonyl-1; or benzisothiazolyl substituted by nitro or bromo, R¹, R² and T¹ to T⁵ having the meanings given for claim
 1. 3. The fibers according to claim 1 wherein in the formula R is hydrogen or methyl.
 4. The fibers according to claim 1 wherein in the formula R is methyl.
 5. The fibers according to claim 1 wherein in the formula X is cyano or carbamoyl.
 6. The fibers according to claim 1 wherein in the formula R² and R⁴ are hydrogen.
 7. The fibers according to claim 1 wherein in the formula R¹ and R³ independently of one another are a phenyl ring containing substituents as defined in claim 1 and R² and R⁴ are hydrogen.
 8. The fibers according to claim 1 wherein in the formulaR is hydrogen or methyl, X is cyano or carbamoyl, R² and R⁴ are hydrogen, R¹ and R³ independently of one another are a phenyl ring containing substituents as defined in claim 1 and D has the meanings given in claim
 1. 9. The fibers according to claim 1, wherein the fibers are cotton fibers.
 10. The fibers according to claim 1, admixed or blended with synthetic fibers.
 11. The fibers of claims 10, wherein the synthetic fibers are polyester fibers. 